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Synthesis and investigation of structural, morphological, magnetic, dielectric

and impedance spectroscopic characteristics of Ni-Zn ferrite nanoparticles

Article  in  Ceramics International · November 2016

DOI: 10.1016/j.ceramint.2016.11.046

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Author’s Accepted Manuscript

Synthesis and investigation of structural,

morphological, magnetic, dielectric and impedance
spectroscopic characteristics of Ni-Zn ferrite
nanoparticles

Shahid Atiq, Maria Majeed, Aqsa Ahmad, S.

Kumail Abbas, Murtaza Saleem, Saira Riaz,
Shahzad Naseem www.elsevier.com/locate/ceri

PII: S0272-8842(16)32044-2
DOI: http://dx.doi.org/10.1016/j.ceramint.2016.11.046
Reference: CERI14134
To appear in: Ceramics International
Received date: 28 June 2016
Revised date: 10 October 2016
Accepted date: 7 November 2016
Cite this article as: Shahid Atiq, Maria Majeed, Aqsa Ahmad, S. Kumail Abbas,
Murtaza Saleem, Saira Riaz and Shahzad Naseem, Synthesis and investigation of
structural, morphological, magnetic, dielectric and impedance spectroscopic
characteristics of Ni-Zn ferrite nanoparticles, Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2016.11.046
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 Synthesis and investigation of structural, morphological, magnetic, dielectric and
impedance spectroscopic characteristics
of Ni-Zn ferrite nanoparticles

Shahid Atiq1,*, Maria Majeed1, Aqsa Ahmad1, S. Kumail Abbas1, Murtaza Saleem2,
Saira Riaz1 and Shahzad Naseem1
1
Centre of Excellence in Solid State Physics, University of the Punjab, Quaid-e-Azam
Campus, Lahore 54590, Pakistan
2
Department of Physics, School of Science and Engineering, Lahore University of
Management Sciences (LUMS), Opposite Sector U, D.H.A., Lahore Cant 54792, Pakistan

Abstract

A series of ferrite samples with general formula Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8
& 1.0) synthesized using sol-gel self-assisted combustion method have been investigated. X-ray
diffraction patterns confirmed the spinel cubic structure of all the samples with Fd3m space
group. Lattice constant, crystallite size, bulk density, and X-ray density increase while porosity
of the samples decreases with increasing Zn contents. Rietveld’s refinement was also carried out
to compare the calculated and observed X-ray diffraction patterns, which subsequently
confirmed the evaluated structural parameters. Irregular shaped grains were mainly decreasing in
size in the series of samples, revealed by images obtained using field emission scanning electron
microscope. A decrease in saturation magnetization was observed with Zn substitution at Ni-site
while coercivity was increased, exhibiting a transition towards hard ferromagnetic behavior. An
increase in remanent magnetization was also evident, mainly attributed to an increase in
magneto-crystalline anisotropy energy. A systematic investigation of frequency dependent
electrical and dielectric properties has also been performed. Incorporation of Zn at Ni-site
resulted in increase in ac conductivity while resistance and reactance of the samples were
decreased. Nyquist and modulus graphs were plotted and their characteristic behaviors were
analyzed.

Keywords: Ni-Zn ferrites; Structural morphology; Magnetic properties; Impedance spectroscopy

1. Introduction

Ferrites are the magnetic ceramics containing Fe2O3 as their major component [1].
Ferrites exist in numerous crystalline forms among which, spinel structure is the most studied.
The spinel crystal structure is associated to the structure of mineral spinel, MgO.Al2O3. Spinel
ferrites contain general molecular formula MO.Fe2O3, where M is a divalent metal ion (Fe2+,
Mg2+, Ni2+, Co2+, Mn2+etc). Spinel ferrite nanoparticles have substantial importance for scientists
to examine their structural, electrical, magnetic and dielectric properties to make them applicable
for technological applications in industries [2]. Owing to their soft magnetic characteristics,
spinel structured ferrites possess low coercivity (Hc) [3], high permeability [4], high electrical
resistance [5] and low eddy current losses [6]. Due to these technically important features, soft
ferrites are the most suitable for manufacturing recording heads, core of power transformers, data
storage, media devices, telecommunication equipment, electronic and microwaves devices [7-9].

In the midst of other ferrites, Ni-Zn ferrites, being a mixed ferrite of Ni and Zn, have a
festive significance. Previous studies on these ferrites have proposed that Ni-ferrites when doped
with Cu, Cr and Zn, enhance electrical and magnetic properties [10]. Spinel structured Ni-Zn
ferrites, [Fe1-x3+Znx2+]A[Ni1-x2+Fe1+x3+]BO4, ‘x’ being inversion degree, belong to Fd3m space
group having 64 tetrahedral (A) and 32 octahedral (B) sites in the unit cell with 32 oxygen ions.
Only one-eighth tetrahedral and one half of the octahedral sites are occupied by metal ions (of
either +2 or +3 valence). A ferrite unit cell has 8 formula units with 56 ions [11]. Zn when
subjected to sintering, lose its position due to which cation vacancies occur and oxygen ions that
are left behind, are compelled to combine with Fe3+ ions forming the Fe2+ ions and hence
increase the charge hopping mechanism [12]. Furthermore, Ni-Zn ferrites are found to have high
saturation magnetization (Ms), low Hc, high permeability [13], high dielectric constant and low
losses [14, 15].

Novel physiochemical properties of single phase spinel ferrites are highly sensitive to
their chemical composition [16], microstructure [17], cation distribution [18], preparation
methodology, sintering temperature and dopant levels [19]. In order to improve their
electromagnetic and dielectric properties, many research groups have doped rare-earth and
transition metals in parent compounds [20]. For instance, electrical properties were immensely
varied when parent compound was doped with Ni, studied using conductance spectroscopy [21].
In this context, the present work focuses on the facile synthesis of Zn-doped NiFe2O4 samples
using sol-gel processing, in order to proceed a systematic investigation of structural, magnetic
and impedance spectroscopic characteristics of this important family of ferrites for technological
applications.

There are obviously several different methods for synthesizing spinel ferrites such as
ball-milling, co-precipitation, hydrothermal precipitation, citrate precursor, auto-combustion,
solid state reaction, microwave hydrothermal process, mechano-chemical and micro-emulsion
route [22-26]. Due to high compositional control and economics involved, in the present work,
sol-gel auto-combustion method is used to get Ni-Zn ferrite nano-particles.

2. Experimental details

Ni-Zn ferrites with a nominal composition of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 &
1.0) were synthesized using sol-gel auto-combustion route. Stoichiometrically weighed amounts
of metals nitrates (MNs), such as nickel nitrate [(Ni(NO3)2.6H2O), ≥ 99.98%], zinc nitrate
[(Zn(NO3)2.6H2O), ≥ 98%], iron nitrate [(Fe(NO3)2.9H2O), ≥ 99.95%], and citric acid [(C6H8O7),
≥ 99%], all purchased from Sigma-Aldrich, were separately dissolved in distilled water, keeping
MNs to citric acid ratio of 1 : 2. The solutions were made and mixed together by taking optimum
volume of distilled water so that the final volume of the solution would be 50 mL. The solution
was then stirred constantly for 2 hrs with constant heating at 95 °C in an ESCO fume hood until
it converted into a xerogel. After the formation of the gel, the stirring was stopped and the
temperature was gradually raised to 300 °C. A continuous heating at this temperature for about
10 min led the xerogel to burn in a self-sustaining auto-combustion reaction and the final product
was a black, homogeneously dried powder. Masses of the dried powder samples were varying
between 2.65 – 2.82 g. An Agate mortar and pestle was used to obtain a very fine powder after
grinding. The powder samples were subsequently calcined at 800 °C for 4 hrs in a muffle furnace
for gaining better microstructure and improving the crystallinity. Finally, the pellets of the ferrite
samples (having 10 mm diameter and 1.2 mm thickness) were prepared using an APEX
hydraulic press using a force of 4 ton. All the characterizations were performed using these pellet
samples.
 The structural analysis and surface morphology of the synthesized samples were
determined using a Bruker D8 Advanced X-ray diffractometer (XRD) utilizing Cu-Kα radiations
having a wavelength of 1.5418 Å and a NovaNano SEM 450 field emission scanning electron
microscope (FESEM), respectively. Magnetic behavior of the samples was determined using a
Lakeshore-7410 vibrating sample magnetometer (VSM). Dielectric measurements of the samples
were performed using a Wayne-Kerr 6500B precision impedance analyzer.

3. Results and discussion

Data obtained from XRD were plotted and indexed by observing the position of each
diffracted line. Firstly, the values of sin2θ were noted for all the diffracted peaks and
subsequently divided with minimum value of sin2θ. After some further manipulations, as
described by Cullity [27], hkl values were assigned to each diffracted line, as shown in Fig. 1.
The hkl values were also matched with the ICSD ref. no. 00-010-0325 which depicted that the
samples had cubic spinel structure, with Fd3m space group. Some minor peaks at 2θ = 32.199°
and 2θ = 49.465° were due to α-Fe2O3 [ICSD ref no. 00-033-0664], which gradually vanished
when Zn was substituted at Ni-site. Furthermore, a slight increase in the peak intensity and a
gradual shift in the peak position towards left were observed as Zn was substituted at Ni-site.
The shift in peak position could rightly be attributed to the difference of ionic radii of the
substituent (0.83 Å) and the host (0.78 Å) [28]. This substitution also resulted in a minute
increase in the lattice constant (a) from 8.335 to 8.351 Å and a small volumetric expansion (V =
a3) in the cubic structure was evident. The crystallite size of the samples was determined by
measuring the full width at half maximum (FWHM) of the highest peak in the diffraction
patterns using the formula, D = 0.9λ/βcosθ, where λ was the wavelength of Cu-Kα radiation (λ =
1.5405 Å), θ was the Bragg’s angle in degrees and β was the FWHM in radians. The crystallite
size was increased from 9.48 to 9.97 nm in the series of samples that could be attributed to the
mismatching of ionic radii of Ni2+- ion (0.78 Å) and Zn2+- ion (0.83 Å), respectively. The slight
increase in crystallite size could be attributed to a quite small difference in the ionic radii of the
substituent and the host site which caused a minor increase in the unit cell volume, ultimately
leading to a small increase in crystallite size. Furthermore, the calculated value of jump length
also increased with the variation of crystallite size. The variation in lattice constant and
crystallite size is shown graphically in Fig. 2 and individual values of all these parameters are
listed in Table. 1.

The data obtained from diffraction was also utilized to determine X-ray density,
( ⁄ , where M is molar mass and NA is Avogadro’s number) which was increased
from 5.41 to 5.48 g/cm3 with the incorporation of Zn ions at Ni-sites. The bulk density was
evaluated using the relation, ⁄ , where m was mass, r was radius and h was thickness
of the pellet samples. also showed an increasing behavior, from 2.99 to 3.55 g/cm3, with Zn
substitution. This in turn helped to determine the porosity using the relation, P = 1 – ρb/ρx, which
decreased from 44.6 to 35.3%. All these evaluated parameters are shown in Table 1. The reason
of decrease in porosity could be credited to the creation of oxygen vacancies when Zn was
substituted in the series of samples [29].

Rietveld’s refinement, a least squares fitting method, was performed in order to minimize
the difference between calculated and observed line profiles of XRD patterns. The diffraction
patterns of all the samples were analyzed using this technique and a suitable model was fitted to
the data using HighScore X′Pert Plus software. In the present case, Pseudo-Voigt profile function
is used in background fitting process [30]. Fig. 3 depicts the Rietveld refined XRD patterns of all
the samples in the series while bottom of each pattern represents the difference plot. Although,
some minor distortions are present in the patterns but due to refined peak positions, the dominant
development of a phase-pure or single phase nature of Ni-Zn ferrites is established.

Quality of fit of the experimental data can be checked with the help of different Rietveld
agreement indices like the percent R profile factor (Rp), the percent weighted profile factor (Rwp),
the percent expected profile factor (Rexp), that must be close to less than 10% and the goodness
of fit (χ2) which is basically the ratio between the weighted R profile and R expected (χ2 =
(Rwp/Rexp)2). The evaluated values of all these parameters are listed in Table 2. The value of χ2
should approach to 2 but should not drop below one. χ2 < 1 means that the standard uncertainties
are overestimated or a lot of parameters are introduced to fit the model. Moreover, χ2 >> 1 shows
that standard uncertainties are underestimated and the model is incomplete and/or wrong. In the
present study, our Rietveld refined values of χ2 and R factors are in good agreement, which
indicates the goodness of refinement of diffraction data of ferrite samples [31, 32].
 Structural morphology of synthesized ferrite samples was visulized using FESEM images
as shown in Fig. 4. The micrographs exhibited regular shaped grains mostly with spherical
morphology, well separated from each other. Well-defined and sharp grain boundaries are
evident in all the samples of the series [33, 34]. Fig. 4 (a) reveals the FESEM image of NiFe2O4
with an average grain size of 60±5 nm. The image also shows scattered black spots associated
with the porosity of the sample. These areas were reduced gradually in the series of samples
resulting in overall reduction in the porosity, well in agreement with the porosity, as evaluated
from the diffraction data. The grain size was also increased gradually and reached to 148±5 nm
for ZnFe2O4 sample. The increasing trend in grain size might also be inferred to the increase of
oxygen vacancies in the subsituted samples [35]. The observed large sized grains consist of large
number of domain walls. The large sized grains might be the agglomerations of small grains
which were not resolved at that corresponding magnification [36].

Fig. 5 depicts the magnetic hysteresis (M-H) loops of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4,
0.6, 0.8 & 1.0) samples obtained using VSM at an applied field of ±6 kOe. Shapes of the loops
reveal a characteristic soft ferromagnetic nature of all the samples [37]. The loops reveal that Ms
value is decreased from 54.809 to 41.769 emu/g as Zn concents were enhanced in the series, as
shown graphically in Fig. 6. The trend could be attributed to the substitution of a diamagnetic
element (Zn2+) at Ni2+ site, having a characteristic ferromagnetic nature. Magnetic ordering in
spinel ferrites is attributed to the interaction among A- and B-sites via oxygen, termed as A–O–B
super exchange interaction. When Zn2+ ions are substituted at Ni2+ sites, a reduction occurs in
this exchange interaction which subsequently decreases further as the Zn2+ contents are incraesed
in the series [38]. As, net dipole moment of the whole lattice is the difference between the
magnetic moments of the A and B sub-lattices which means M = MA-MB, where MA and MB are
the net magnetization of A and B sites, respectively. The weakening of the superexchange
interaction among A–O–B thus leads to a gradual decrease in net magnetization for the samples
with incraesed Zn contents.

On the other hand, Hc and Mr in the Ni-Zn ferrite samples were increased as Zn contents
were increased which shows that samples are moving towards the hard ferromagnetic behavior.
With the increase in grain size, large number of domain walls are normally expected within the
grains. The magnetization and demagnetization caused by domain wall movement need more
energy compared to the energy required for rotation of domains. In this way, the contribution of
domain walls to the magnetization and demagnetization is more than that of domain rotation, and
hence Hc increases as the grain size is increased [39]. The increasing behavior can also be
explained on the basis of decrease in magnetocrystalline anisotropy. The value of
magnetocrystalline anisotropy constant is negative for both Ni and Zn ferrites. The sum of their
individual anisotropies gives the total anisotropy, which becomes more in case of Zn. This is the
reason of increasing Hc with increasing Zn concentration, as exhibited by Fig. 6. The determined
values of Ms, Hc and Mr of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples have been
shown in Table 3. In addition, the decrease in Ms and, increase in Hc and Mr could also be
attributed to the lattice defects and random orientation of spins in addition to the weaker super
exchange mechanism [39].

Fig. 7(a) shows the variation of real dielectric constant (ε') as a function of frequency for
the samples at room temperature (RT) in the frequency range from 100 Hz to 20 MHz. It is clear
from Fig. 7(a) that ε' shows dispersion curves with frequency. For all samples, the value of ε' is
high at low frequency and then it decreases as the frequency increases, and finally becomes
saturated at high frequency. This type of dispersion in ε' plot is credited to the Maxwell-Wagner
type of interfacial polarization in agreement with the Koop’s phenomenological theory [40].
According to these theories, the dielectric structure of ferrite material is considered to be
composing of two layers: grains and grain boundaries, which act like two layers. Grains can be
considered as areas having low electrical resistance due to perfect crystalline characteristics,
while on the other hand grain boundaries are the regions having high resistance. Maxwell-
Wagner interfacial polarization occurs in the grain boundaries due to the charge accumulation in
these higher resistive boundaries. This polarization occurs in all heterogeneous polycrystalline
materials. At higher frequencies, this polarization diminishes and the value of dielectric constant
becomes almost constant. Furthermore, the electronic exchange between the substituted ions
plays an important role in the dielectric and conduction properties of the ferrites. Since the
substitution is occurring at tetrahedral sites, so the electronic exchange phenomenon due to Ni
and Zn ions can give rise to local displacement of charges in the direction of the applied field.
These local displacements then determine the polarization mechanism and give high values of ε'
at low frequencies. Beyond a certain frequency of the external electric field, these local
displacements cannot follow the alternating field and thus relaxes which causes the ε' to saturate.
Hence, the polarization decreases.

It can also be seen that ε' curve relaxes at lower frequencies with the increase in Zn
contents depicting lower probability of dipolar orientation. It can be said that as the Zn contents
increase, the mobility of the charge carriers decreases which in turn causes the local
displacements of charges to decrease even further at lower frequencies. Thus, the dipoles relax at
lower frequency causing the ε' curve to saturate.

Fig. 7 (b) depicts the variation of ε' with Zn contents in the samples at RT. The ε'
decreases with the increasing concentration of Zn. The dispersion in ε' for all samples can be
explained on the basis of reduction in particle size and an increase in the porosity of the samples
with increase in Zn contents [41]. As a result, the surface area with high resistive nature i.e. the
grain boundary region increases along with poor contact with the neighboring grains. More
structural defects are introduced due to increase in porosity and grain boundaries which cause
accumulation of charge carriers at the interfaces. This lowers the carrier mobility which in turn
lowers the dipolar orientations with the applied variations in ac electric field. Consequently, the
dielectric polarization decreases with the increase in Zn contents.

Furthermore, this composition dependent behavior of Ni-Zn ferrites can also be explained
on the basis of inverse spinel structure [42]. In the samples under study, the presence of Ni3+/Ni2+
ions lead to the formation of p-type charge carriers (holes). While in these ferrites, n-type charge
carriers (electrons) are also present due to the presence of Fe3+/Fe2+ ions. The local displacements
of these carriers in the direction of the applied field contribute to the polarization mechanism.
The maximum value of ε' for Ni-ferrite is obtained because maximum number of Fe3+ ions are
present at B site, thus showing high hopping rates as the contribution from these n-type carriers
is high as compared to p-type carriers. With the Zn substitution, Fe3+ ions are replaced which
depletes the number of Fe ions available for the conduction process, resulting a decrease in the
probability of the following exchange mechanism:

Ni2+ + Fe3+ ↔ Ni3+ + Fe2+

The behavior of tangent loss (tan δ = 1/2πfRC) and dielectric loss factor (ε" = ε' tan δ)
are similar to ε'. It is observed from Fig. 8 (a) and (b) that tangent loss and dielectric loss factor
(ε") have high values at low frequencies while decrease with the increment in frequency and
becomes independent at high frequencies. Tangent loss is the measure of energy absorption in
the dielectric medium. These results are in accordance with the Koop’s phenomenological theory
and therefore, it is expected that the energy losses are high at low frequency while they are low
at high frequency region. The behavior of these losses can be understood on the basis of
polarization resonance with applied field. According to Koop’s theory, the grain boundaries have
larger value of resistance in the low frequency region. Therefore, higher energy is required for
hopping of electrons from one site to another. Due to this reason, the loss is large at this value of
frequency. In high frequency region, resistivity is small and grains play dominant role. Hence, a
low energy is required for electrons to shift between two ions at different sites. So the energy
loss is small [43].

The decrease in the values of tanδ and ε" at different frequencies, with increasing Zn
contents at Ni-sites is shown in Fig. 9 (a) and (b), respectively. In spinel ferrites as explained
above, the dielectric and conduction mechanism are strongly related to each other. The dielectric
loss in these materials is attributed to the strong dielectric dispersion because of the interfacial
polarization. As the Zn contents increase, the grain size decreases, lowering the carrier mobility
which also reduces the energy storage mechanism. This process reduces the losses and thus low
tanδ and ε" values are obtained at higher Zn contents.

In order to observe the conduction behavior and to determine the parameters that might
control the conduction mechanism of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples, ac
conductivity data were plotted against frequency range of 100 Hz to 20 MHZ at RT. Electrical
conduction mechanism is related to the electron and polaron hopping mechanism which acts as
hopping channels An increase in frequency facilitates the conductive channels to become more
active by promoting the hopping of charge carriers. The increase in ac conductivity
measurements depicts that the conduction mechanism occurs due to small polaron hopping [44].

Furthermore, with the addition of Zn contents, two distinct regions are visible in the
conductivity spectra for all the substituted and unsubstituted samples. In region I, the
conductivity curve is pure frequency independent, while in region II, the conductivity curve
starts increasing. However, there is a shift of these conductivity regions towards the lower
frequency side and also the conductivity increases with respect to Zn contents. We take help
from the Jonscher’s power law, as given in Eq. 1, to understand the ac conductivity process:

(1)

The first term on the right side of the power law is the frequency independent term at low
frequencies and the second term is the frequency dependent term at high frequencies. The first
term in the power law is designated as dc conductivity which is found to decrease as the Zn
contents increase, as shown in Fig. 10. This feature demonstrates that the conductivity
mechanism for substituted samples is different from the un-substituted samples. At high
frequencies, due to the dielectric relaxation caused by the localized charge carriers, conductivity
increases. Here, in the second term, A is the constant, ω is the angular frequency (2πf) and n is
the slope of the frequency dependent conductivity curve. The values of n, depending on Zn
concentration, have been found by using the slopes of the conductivity curves. The region I
shows no change in the values of n with Zn contents, which shows a non-equilibrium occupancy
of trap charges. Whereas, in region II, the values of n are found to be increasing from 0432 to
0.745. This increasing value of n depicts that the conduction arises in region II due to short range
translational hopping of small polarons [41].

The impedance analysis is a significant technique to study the electrical properties of

ceramics. Microstructure is the top the most factor which influences the impedance. To get more
insight into the electrical properties, the variation of real part (Z') and imaginary part of
impedance (Z'') of Ni1-xZnxFe2O4 ((x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) with frequency at RT has
been observed and is shown in Fig. 11 (a, b). The magnitude of Z' was found to be higher at
lower frequency range. This behavior could be explained in terms of the enhanced hopping of
charge carriers between the localized ions. The decrease in real and imaginary parts of the
impedance can be attributed to the conductivity at high frequency. As the imaginary part, Z''
explains the reactance of capacitor, it also decreases with frequency which indicates the presence
of space charge polarization. The imaginary plot usually shows an emergence of a broad peak
which suggests the occurrence of relaxation mechanism. As it can be seen that no peak is visible
in Z'' plot, which means Nyquist plot of these samples will not generate complete semi-circles is
this range of frequency. The calculated values of grain boundary resistance (Rgb) and capacitance
(Cgb) are listed in Table 4.
Complex impedance analysis is a significant technique to distinguish the transport
characteristics occurring between the grains and grain boundaries, and explains the changes
observed in the dielectric permittivity, dielectric losses and conductivity of a certain material
[42]. The impedance of material can be measured by series or parallel combination of RC
equivalent circuit. Electrical properties of materials are also calculated in terms of complex
impedance (Z*). Nyquist graph elaborates the impedance behavior of different ceramic samples
and depicts different conduction and relaxation processes. The Nyquist plot of complex
impedance of the synthesized Ni-Zn ferrite samples is shown in Fig. 12. The varying patterns of
all the samples consist of semicircular arcs with their centers lying below the real axis. This
indicates a non-Debye type relaxation phenomenon in Ni-Zn ferrites. The characteristic shapes
of the curves shown in Fig. 12 provide interesting information such as giving an indication of
existence of microstructural electro-active regions which are grain boundaries in the present
case.

The dielectric data measured over an extended frequency range at RT is further

investigated using complex modulus spectroscopy. Modulus spectroscopy is useful for analyzing
the relaxation phenomenon in electrically and ionically conducting materials and to determine
the electrode polarizing effects which annihilate effectively [45]. The complex modulus is
inversely related to complex dielectric constant by the relations:

M '   ' /( ' 2  "2 ) (2)

M "   " /( ' 2  "2 ) (3)

where M' is the real part and M" is the imaginary part of complex electric modulus. Fig. 13 (a)
shows variation of the real part of electric modulus for all compositions of Zn doped Ni ferrites
with frequency. M' shows a significant dispersion in lower frequency region and gradually
increases and becomes constant at higher frequency. The dispersion obtained in this plot
corresponds to the short range mobility of the charge carriers. Fig. 13 (b) depicts the variation of
M" with frequency, which shows a broad peak for each sample indicating the existence of
relaxation mechanism for Ni-Zn ferrites. The shifting of peaks towards a lower frequency with
the addition of Zn contents signifies the hopping of charge carriers at higher frequency [45]. This
hopping was also responsible for high frequency conduction mechanism. At lower frequencies,
these charge carriers are confined to their potential wells [46]. The distribution of these
relaxation peaks can be attributed to the interaction of the ions involved.

4. Conclusion

A series of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) soft ferrite samples was
prepared using sol-gel auto-combustion technique and the as-prepared powder samples were
calcined at 800 °C for 2 hrs in order to develop the crystal structure. XRD confirmed the spinel
cubic structure of all the prepared samples. A slight increase in the lattice constant from 8.335 to
8.351 Å and crystallite size 9.48 to 9.97 nm was observed mainly attributed to the difference of
the ionic radii of the substituent and the host. The Rietveld’s refinement technique was also
utilized to refine the diffraction patterns and the goodness of fit values were also in good
agreement. Mostly, the grains were regular in shape with sharp boundaries while the average
grain size was reduced from 250 to 100 nm, in the series of samples. The trend of porosity as
evident from the FESEM images were well in agreement as determined from the diffraction data.
A gradual transition from hard to soft ferromagnetic characteristics was observed with Zn
substitution at Ni-site, as Ms was decreased, while Hc and Mr were increased. Frequency
dependent dielectric properties revealed that due to incorporation of Zn, ac conductivity was
increased mainly attributed to increase in charge hopping and was extremely particle size
dependent. This behavior was explained on the basis of Koop’s phenomenological theory and
Maxwell-Wagner interfacial two layer model. Impedance spectroscopy and electric modulus
studies were also conducted in a wide frequency range of 100 Hz to 20 MHz. The complex
modulus studies revealed the presence of non-Debye type relaxation phenomenon in the ferrite
samples. The Nyquist plot demonstrated that the grain boundary behavior was responsible for the
polarization in the prepared samples.

Acknowledgement
The authors are thankful to Higher Education Commission (HEC) Pakistan for financing
this research under HEC project NRPU-2471.
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 Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 &1.0)

(311)

(440)
(220)

(511)
Intensity (Arb. units)

(400)
(222)

(422)

(533)
x = 1.0

x = 0.8

x = 0.6
x = 0.4
x = 0.2

x = 0.0
* *
20 30 40 50 60 70 80
2 (Degree)

Fig. 1 Indexed XRD patterns of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 &1.0) samples at room
temperature. Impurity peaks are indicated by *
 8.352 10.1
Lattice Constant

Crystallite size, D (nm)

Lattice Constant, a (Å)

Crystallite size
8.349 10.0
8.346 9.9

8.343 9.8

8.340 9.7

8.337 9.6

8.334 9.5
0.0 0.2 0.4 0.6 0.8 1.0
Zn contents (x) in Ni1-xZnxFe2O4

Fig. 2 Variation of lattice constant (a) and crystallite size (D) with Zn contents
Fig. 3 Rietveld refined XRD patterns of Ni1-xZnxFe2O4 (x = 0.2, 0.6, 0.8 & 1.0) samples at room
temperature. Bottom lines in each pattern show the difference between experimental and refined
data
Fig. 4 FESEM images of Ni1-xZnxFe2O4 for (a) x = 0, (b) x = 0.2, (c) x = 0.4, (d) x = 0.6,
(e) x = 0.8, and (f) x = 1.0 at 10,000x magnification
 Saturation Magnetization (emu/g)

Ni1-xZnxFe2O4
60
x = 0.0
x = 0.2
40 x = 0.4
x = 0.6
20 x = 0.8
x = 1.0
0

-20

-40

-60
-6000 -4000 -2000 0 2000 4000 6000

Applied Field (Oe)

Fig. 5 Magnetic hysteresis (M-H) loops of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 &1.0)
samples at room temperature
 Saturation Magnetization (emu/g)

Saturation Magnetization 300

54 Coercivity
250

Coercivity (Oe)
51
200
48
150
45
100
42
50
0.0 0.2 0.4 0.6 0.8 1.0
Zn Contents (x) in Ni1-xZnxFe2O4

Fig. 6 Saturation magnetization and coercivity as a function of Zn contents

 135
(a) Ni1-xZnxFe2O4 x = 0.0
75 (b) Ni1-xZnxFe2O4 f1 = 1 kHz
f2 = 11 kHz
x = 0.2

Dielctric constant ()

120
Dielctric constant ()

f3 = 110 kHz
x = 0.4
x = 0.6 70 f4 = 1 MHz
f5 = 10 MHz
105 x = 0.8 f6 = 20 MHz
x = 1.0 65
90
60
75
55
60
50
45
3 4 5 6 7 0.2 0.4 0.6 0.8 1.0
log f Zn contents (x)

Fig. 7 Variation of dielectric constant with (a) frequency, and with (b) Zn contents for
Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples at room temperature
 Imaginary dielectric constant ()
0.10 (a) Ni1-xZnxFe2O4 x= 0.0 20 (b) Ni1-xZnxFe2O4 x = 0.0
x= 0.2 x = 0.2
0.09 x= 0.4 18 x = 0.4
Tangent loss (tan

x= 0.6 x = 0.6
0.08 x= 0.8
16 x = 0.8
x = 1.0
0.07
x= 1.0
14
0.06 12
0.05 10
0.04 8

0.03 6

0.02 4
3 4 5 6 7 8 3 4 5 6 7
log f log f

Fig. 8 Variation of (a) tangent loss, and (b) imaginary dielectric constant with frequency of
Ni1-xZnxFe2O4(x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples at room temperature
 Imaginary dielectric constant ()
0.09 (a) Ni1-xZnxFe2O4 f1= 1kHz
(b) Ni1-xZnxFe2O4 f1= 1kHz
f1= 11kHz 14 f2 = 11kHz
0.08 f1= 110kHz f3 = 110kHz
Tangent loss (tan

f1= 1MHz f4 = 1MHz

0.07 f1= 10MHz 12 f5 = 10MHz
f1= 20MHz f6 = 20MHz
0.06 10
0.05
8
0.04
6
0.03
0.02 4
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Zn contents (x) Zn contents (x)

Fig. 9 Variation of (a) tangent loss and, (b) imaginary dielectric constant with Zn contents for
Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples at room temperature
 -1
Sm

3 x = 0.0 Ni1-xZnxFe2O4
x = 0.2
(,

3 x = 0.4
x = 0.6
20

x = 0.8
2
ac Conductivity * 10

x = 1.0

0
3.2 4.0 4.8 5.6 6.4
log f
Fig. 10 Frequency dependent ac conductivity of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 &1.0)
ferrite samples
 140M x = 0.0
Ni1-xZnxFe2O4 Ni1-xZnxFe2O4 x = 0.0

Imaginary impedance (Z), 

500k
Real impedance (Z'), 

x = 0.2 x = 0.2
120M x = 0.4 x = 0.4
(a) x = 0.6 400k (b) x = 0.6
100M x = 0.8 x = 0.8
x = 1.0 x = 1.0
80M 300k

60M
200k
40M
100k
20M

0 0
3 4 5 6 7 3 4 5 6 7
log f log f

Fig. 11 Dependence of (a) real and (b) imaginary part of impedance on frequency for all samples
of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) ferrites
 Imaginary impedance (Z)

-5000K Ni1-xZnxFe2O4

-4000K

-3000K
x = 0.0
-2000K
x = 0.2
x = 0.4
-1000K x = 0.6
x = 0.8
0K x = 1.0

0K 150K 300K 450K 600K

Real impedance (Z)

Fig. 12 Frequency dependent Nyquist plot for Ni1-xZnxFe2O4(x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0)
samples at room temperature

Error! Not a valid embedded object.

Table 4 Values of grain boundary resistance (Rgb) and capacitance (Cgb) of Ni1-xZnxFe2O4 (x = 0.0, 0.2,
0.4, 0.6, 0.8 & 1.0) samples

Zn Rgb (kΩ) Cgb (pF)

contents
x = 0.0 764.993 0.270
x = 0.2 773.161 0.274
x = 0.4 978.293 0.289
x = 0.6 993.247 0.290
x = 0.8 1007.231 0.296
x = 1.0 1014.038 0.299
 Table 1 Variation of lattice constant, crystallite size, jump length at site-A and site-B, bulk
density, X-ray density and porosity of the Ni1-x ZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples

Zn Lattice Crystallite Jump Length Bulk X-ray Porosity/

contents/ constant/a size/D density/ρb density/ρx P
(nm) LA (Å) LB (Å) (%)
x (Å) (g/cm3) (g/cm3)
0.0 8.335 9.48 3.6091 2.9468 2.99 5.41 44.6
0.2 8.338 9.55 3.6104 2.9479 3.07 5.42 43.3
0.4 8.342 9.57 3.6122 2.9493 3.15 5.43 41.9
0.6 8.344 9.72 3.6130 2.9500 3.38 5.46 38.0
0.8 8.350 9.78 3.6156 2.9521 3.54 5.47 35.4
1.0 8.351 9.97 3.6161 2.9525 3.55 5.48 35.3
Table 2 Rietveld agreement factors (R expected, R profile, Weighted R profile and Goodness of fit) of
Ni1-x ZnxFe2O4 (x = 0.2, 0.4, 0.6, 0.8 & 1.0) samples

Zn R expected R profile Weighted R profile Goodness of Fit

contents Rexp (%) Rp (%) Rwp (%) χ2
/x
0.2 28.04669 30.05441 38.77718 1.918
0.4 32.63097 34.21541 42.54325 1.700
0.6 27.49784 31.86498 39.61893 2.074
0.8 28.71031 31.15279 39.35019 1.879
1.0 22.13018 23.57714 28.99180 1.716
 Table 3 Values of Ms, Hc and Mr of Ni1-xZnxFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1.0) samples

Zn Ms (emu/g) Hc (Oe) Mr (emu/g)

contents
x = 0.0 54.809 71.304 1.755
x = 0.2 51.280 90.082 2.421
x = 0.4 48.801 102.84 2.433
x = 0.6 45.107 184.16 5.190
x = 0.8 43.438 236.76 6.972
x = 1.0 41.769 289.36 8.753

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